Pesticidal 1-polyarylimidazoles

ABSTRACT

A compound of formula (I): ##STR1## compositions containing them and methods of use to control pests.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.08/963,631, filed Nov. 4, 1997, now U.S. Pat. No. 5,922,884, whichclaims the priority of U.S. Provisional Patent Application Ser. No.60/030,128, filed Nov. 4, 1996. Both prior applications are incorporatedby reference herein in their entireties and relied upon.

The invention relates to new 1-arylpyrazoles and derivatives thereofwhich have some valuable properties either as pesticides or asintermediates to make other pesticides. The invention further pertainsto compositions of said compounds and methods, using said compoundseither as intermediates to make other pesticides, or for the control ofpests particularly insects, in particular to the application of saidcompounds or compositions in agricultural methods of use or for animalprotection, particularly as pesticides, for controlling arthropods.

International Patent Publication No. WO 87/03781 and European PatentPublication No. 295117, 154115, 201852 describe insecticidal1-(substituted phenyl) pyrazoles. Other prior art is also found in thetext of these patent applications or the patents issued therefrom.

International Patent Publications No. WO 93/06089 and WO 94/21606 alsodescribe insecticidal 1-(4--SF₅ substituted phenyl) heterocycles whichmay be pyrroles as well as imidazoles or pyrazoles. The teaching ofthese patents is not substantially different from International PatentPublication No. WO 87/03781 or from European Patent Publication No.0295117 as far as pyrazoles are concerned.

It is an object of the present invention to provide new pesticidalcompounds of the 1-arylpyrazole family together with processes for theirpreparation.

Another object of the present invention is to provide pesticidalcompositions and pesticidal methods of use of the pesticidal pyrazolecompounds against arthropods, especially insects, particularly inagricultural or horticultural crops, forestry, veterinary medicine orlivestock husbandry, or in public health.

A third object of the present invention is to provide very activecompounds with broad spectrum pesticidal activity, as well as compoundswith selective special activity, e.g., aphicidal, miticidal, foliarinsecticidal, soil insecticidal, systemic, antifeeding or pesticidalactivity via seed treatment.

A fourth object of the present invention is to provide compounds withsubstantially enhanced and more rapid activity, especially againstinsects and more particularly insects in their larval stages.

A fifth objective of the present invention is to provide compounds withgreatly improved (faster and greater) penetration into pest species whentopically applied and to thus provide enhanced movement of the compoundsto the pesticidal site(s) of action within the pest.

These and other objectives of the invention are met in whole or part andshall become readily apparent from the description of the presentinvention which follows.

The invention thus relates to compounds having the general formula (I):##STR2## wherein: X is N or C--R₂ ;

Y is N or C--R₃ ;

W is N or C--R₄ ;

R₂ and R₃ are independently selected from H, halogen, hydroxy, alkyl,cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN, NO₂, --S(O)_(n) R₈,alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl,dialkylarninocarbonyl, hydroxycarbonyl, aminosulfonyl,alkylaminosulfonyl, and dialkylaminosulfonyl;

R₄ is H, halogen, alkyl, alkoxy, CN, NO₂, haloalkyl, haloalkoxy,thiocyanato, formyl, alkylcarbonyl, --CH═N--OH, --CH═N--O-alkyl,--S(NH₂)(═NH), --S(O)_(n) R₈, mercapto, haloalkylcarbonyl, or a --S--radical so that two molecules are bound together to form a disufidecompound;

R₅ is hydrogen, halogen, --NR₉ R₁₀, --N═CR₁₁ R₁₉, --S(O)_(n) R₈, formyl,alkylcarbonyl, haloalkylcarbonyl, cyano, alkyl, haloalkyl, hydrazino,alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl;

R₈ is alkyl or haloalkyl, alkenyl or alkynyl, or a cycloalkyl ringcontaining 3 to 5 carbon atoms;

R₁₁ is H, or alkyl;

R₁₉ may also be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy,alkylthio, amino, monoalkylamino, dialkylamino, or R₁₉ is phenyl,thienyl, pyridyl or furyl, each of which is unsubstituted or substitutedwith alkyl, haloalkyl, halogen, NO₂, CN, alkoxy, haloalkoxy, OH,alkylcarbonyl, alkylcarbonyloxy;

R₉ and R₁₀ independent of one another, are H, alkyl, haloalkyl,alkylcarbonyl, haloalkylcarbonyl, R₈ S(O)_(n), formyl, alkenyl, alkynyl,alkoxycarbonyl, alkylthiocarbonyl, aroyl; or are joined so as togetherform a divalent radical having 4 to 6 atoms in the chain, this divalentradical being alkylene, alkyleneoxyalkylene or alkyleneamdinoalkylene,preferably to form a morpholine, pyrrolidine, piperidine or piperazinering; the alkyl portion of R₉ and R₁₀ may be substituted by R₇ ;

R₇ is cyano, nitro, alkoxy, haloalkoxy, R₈ S(O)_(n), --C(O)alkyl,alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,--CO₂ H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl ordialkylaminosulfonyl;

Z is N or C--R₁₆ ;

n is zero, one or two;

R₁₂, R₁₃, R₁₅, R₁₆, are independently selected from hydrogen, halogen,alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy,haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl,haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl,alkylcarbonyl, alkoxycarbonyl;

R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ are hydrogen, halogen, alkyl, haloalkyl,cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy,haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, andalkoxycarbonyl, SF₅, R₈ S(O)_(n) ; preferably R₂₄ is halogen, haloalkylor haloalkoxy; or R₂₂ and R₂₃ or R₂₃ and R₂₄ or R₂₅ and R₂₆ may also betogether a divinylidene group (--CH═CH--CH═CH--) or a methylene diether(--O--CH₂ --O--) or halomethylene diether (--O--CF₂ --O--) so as to forma cyclic ring vicinal to the phenyl ring; or pesticidally acceptablesalts thereof.

By the term "pesticidally acceptable salts" is meant salts the anionsand cations of which are known and accepted in the art for the formationof pesticidally acceptable salts. Preferably such salts are watersoluble. Suitable acid addition salts formed from compounds of formula(I) containing an amine group, include salts with inorganic acids forexample hydrochlorides, phosphates, sulfates and nitrates, and saltswith organic acids for example acetates. Suitable salts with basesformed from compounds of formula (I) containing a suitably acidic groupinclude alkali metal (for example sodium or potassium) salts, ammoniumsalts and organic amine (for example diethanolamine or morpholine)salts.

In the present invention, some words are used in a specific sense:

The term "lower alkyl-S(O)_(n) " means a radical of the formula--S(O)_(n) -- lower alkyl. The term "R₁₀ S(O)_(n) " means a radical ofthe formula --S(O)_(n) R₁₀. The term "aminocarbonyl" means a carbamoylradical, that is, a radical of the formula --C(O)NH₂. Similarly, theterm "alkylaminocarbonyl" means an alkylcarbamoyl radical, that is, aradical of the formula --C(O)--NH-alkyl; and the term"dialkylaminocarbonyl" means a dialkylcarbamoyl radical, that is, aradical of the formula --C(O)--N(alkyl)₂ in which the alkyl moieties canbe the same or different. The term "aminosulfonyl" means a sulfamoylradical, that is, --SO₂ NH₂. Similarly, the term "alkylaminosulfonyl"means an alkylsulfamoyl radical, that is, a radical of the formula --SO₂NH-alkyl; while the term "dialkylaminosulfonyl" means a dialkylsulfamoylradical, which has the formula --SO₂ N(alkyl)₂ wherein the alkylmoieties can be the same or different.

The term "halo" before the name of a radical means that this radical ispartially or completely halogenated, that is to say, substituted by F,Cl, Br, or I, in any combination, preferably by F or Cl. The term"halogen" means F, Cl, Br or I. The term "lower" before the name of aradical having a carbon skeleton means that this carbon skeleton hasless than 6 carbon atoms. When the name of any substituent is repeated,it keeps the same meaning unless otherwise specified. The term "aryl"designates a carbon and/or heteroatom-containing aromatic radical whichis preferably phenyl optionally substituted with one or moresubstituents selected from halogen, methyl and methoxy, especiallyphenyl, halophenyl, tolyl or xylyl. The term "aroyl" designates acarbonyl aromatic radical, that is, aryl--C(O)--, which is preferably abenzoyl, methylbenzoyl, halobenzoyl or xylylcarbonyl radical. The term"acyl" designates an alkylcarbonyl radical. The various individualradicals (such as alkyl, alkenyl, alkynyl, alkoxy and alkylene or thelike) generally contain up to six carbon atoms.

A preferred class of compounds of formula (I) is that wherein

X is N;

Y is C--R₃ ;

W is C--R₄ ;

R₃ is H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy,haloalkoxy, CN, NO₂, --S(O)_(n) R₈, alkylcarbonyl, alkoxycarbonyl,aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,hydroxycarbonyl, aminosulfonyl, alkylaminosulfonyl,dialkylaminosulfonyl;

R₄ is H, halogen, alkyl, alkoxy, CN, NO--, haloalkyl, haloalkoxy,thiocyanato, formyl, alkylcarbonyl, --CH═N--OH, --CH═N--O-alkyl,--S(NH₂)(═NH), --S(O)_(n) R₈, mercapto, haloalkylcarbonyl, or a --S--radical so that two molecules are bound together to form a disufidecompound;

R₅ is hydrogen, halogen, --NR₉ R₁₀, --N═CR₁₁ R₁₉, --S(O)_(n) R₈, formyl,alkylcarbonyl, haloalkylcarbonyl, cyano, lower alkyl, hydrazino,alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl,preferably, amino--NR₉ R₁₀ ;

R₈ is alkyl or haloalkyl, alkenyl or alkynyl; or a cycloalkyl ringcontaining 3 to 5 carbon atoms; preferably R₈ is lower alkyl;

R₁₁ is H or alkyl;

R₁₉ may also be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy,alkylthio, amino, monoalkylamino, dialkylamino;

or R₁₉ is phenyl, thienyl, pyridyl or furyl, all of them beingoptionally substituted with alkyl, haloalkyl, halogen, NO₂, CN, alkoxy,haloalkoxy, OH, alkylcarbonyl, alkylcarbonyloxy;

R₉ and R₁₀ are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R₈--S(O)_(n), formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl,aroyl; or are joined so as together form a divalent radical having 4 to6 atoms in the chain, this divalent radical being alkylene,alkyleneoxyalkylene or alkyleneaminoalkylene, preferably to form amorpholine, pyrrolidine, piperidine or piperazine ring; the alkylportion of R₉ and R₁₀ may be substituted by R₇ ;

R₇ is cyano, nitro, alkoxy, haloalkoxy, R₈ S(O)_(n), --C(O)alkyl,alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,--CO₂ H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl ordialkylaminosulfonyl;

n is zero, one or two;

Z is N or C--R₁₆ ;

R₁₂, R₁₃, R₁₅, R₁₆, are separately hydrogen, halogen, alkyl, haloalkyl,cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy,alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl,haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl,alkoxycarbonyl;

R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ are halogen, alkyl, haloalkyl, cyanoalkyl,cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl,formyl, alkylcarbonyl, thioamide, amide, and alkoxycarbonyl, SF₅, R₈S(O)_(n), preferably, R₂₄ is halogen, haloalkyl or haloalkoxy; or R₂₂and R₂₃ or R₂₃ and R₂₄ or R₂₅ and R₂₆ may also be together adivinylidene group (--CH═CH--CH═CH--) or a methylene diether (--O--CH₂--O--) or halomethylene diether (--O--CF₂ --O--) so as to form a cyclicring vicinal to the phenyl ring; or a pesticidally acceptable saltthereof.

Another preferred class of the compounds of formula (I) are those withone or more of the following features wherein:

X is N or C--R₂ ;

Y is N or C--R₃ ;

W is N or C--R₄ ;

R₃ is CN or halogen;

R₄ is H, halogen, formyl, or --S(O)_(n) R₈ ;

R₅ is hydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, or --NR₉ R₁₀ ;

R₈ is methyl, ethyl, --CF₃, --CFCl₂, --CF₂ Cl;

R₁₂ and R₁₆ are independently selected from F, Cl, Br and H;

R₁₃ and R₁₅ are H;

R₂₄ is --CF₃, --OCF₃, --CHF₂, --S(O)_(n) CF₃, --CFCl₂, --CF₂ Cl, --OCF₂Cl, --OCFCl₂, Cl, Br or F; or

Z is CCl, CF, CBr or N.

A further especially preferred class of compounds are those wherein:

X is N;

Y is C--R₃ ;

W is C--R₄ ;

R₁₂ and R₁₆ are Cl or Br;

R₁₃ and R₁₅ are H;

R₂₄ is --CF₃, --OCF₃ or Br;

R₅ is amino;

R₉ and R₁₀ are H, alkyl or alkylcarbonyl;

R₈ is methyl or ethyl or CF₃, CCl₂ F, CClF₂ ; and

R₃ is CN or halogen.

For the above preferred compounds, there are optimum combinations ofsubstituent groups.

Further, preferred S(O)_(n) R₈ substituents in formula (I) are:methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl,ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio,cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl,isopropylthio, trifluoromethylthio, trifluoromethylsulfinyl,trifluoromethylsulfonyl, dichlorofluoromethylthio,dichloromethylsulfinyl, dichloromethylsulfonyl,chlorodifluoromethylthio, chlorodifluoromethylsulfonyl orchlorodifluoromethylsulfinyl.

Some compounds are useful as intermediates to make other pesticides,others are useful directly as pesticides. Compounds wherein R₂₃ or R₂₄or R₂₅ is formyl are preferred as intermediates as well as compoundswherein R₅ is H or compounds wherein simultaneously R₄ is nothalogenated and R₂₂ and R₂₃ and R₂₄ and R₂₅ and R₂₆ are H.

The compounds of general formula (I) can be prepared by the applicationor adaptation of known methods (ie., methods heretofore used ordescribed in the chemical literature including the Chemical Abstracts)employing as starting material the compounds of formula (II) ##STR3##

wherein the various substituents have the same meaning as in formula (I)and halo is a halogen atom, preferably bromine or iodine.

The compounds of formula (II) can be prepared by methods or processessimilar to those described in International patent applications WO87/03781, 93/06089, 94/21606, in European patent applications 295117,403300, 385809, 0500209, 679650, 285,893, and 780,381, U.S. Pat. Nos.5,232,940, 5,236,938, 5,187,185, 5,223,525 and German Patent application19511269 or by other methods known to the skilled addressee. The skilledaddressee understands and is generally knowledgeable of ChemicalAbstracts.

According to a first method of preparation of compounds of formula (I)from compounds of formula (II), a compound of formula (II) is caused toreact with a boric acid or ester, preferably in presence of a couplingcatalyst, so as to form a compound of formula (III) ##STR4##

wherein the substituents have the same meaning as previously indicated,and B(OR₃₀)₂ represents a boric acid or ester group (R₃₀ is preferablyhydrogen, alkyl, or a divalent lower alkylene radical such that two R₃₀O radicals may form a cyclic borate ester),

said compound (III) being, in a second step, caused to react with acompound of formula (VI) ##STR5##

wherein R₂₀ is bromine or iodine or O--SO₂ CF₃.

The first step of this first process is generally and preferablyconducted in an organic solvent, for example an hydrocarbon such astoluene or xylene; an amide such as dimethylformamide orN-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethaneor 2-methoxyethylether; the temperature is generally between 50° C. and150° C.; utilizing as catalysts organic derivatives of palladiumincluding palladium acetate, tetrakis(triphenylphosphine)palladium(0) orPd₂ (dibenzylidene acetone)₃, generally in the presence of a base suchas an alkaline hydroxide or carbonate acetate ion or an amine. The boronderivative used as a reactant with the compound of formula (II) ispreferably a cyclic diboron ester or acid of formula (R₃₀ O)₂B--B(OR₃₀)₂.

The second step of this first process is advantageously conducted in anorganic solvent, for example an hydrocarbon such as toluene or xylene;an amide such as dimethylformamide or N-methylpyrrolidone; an ether suchas tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; thetemperature is generally between 50° C. and 150° C.; utilizing ascatalysts organic derivatives of palladium including palladium acetate,tetrakis(triphenylphosphine)palladium(0) or Pd₂ (dibenzylideneacetone)₃, generally in the presence of a base such as an alkalinehydroxide or carbonate acetate ion or an amine.

According to another method of preparation of compound of formula (I), acompound of formula (II) is caused to react with a compound of formula(IV): ##STR6##

wherein the substituents have the same meaning as previously indicated.

The process is generally and preferably conducted in an organic solvent,for example an hydrocarbon such as toluene or xylene; an amide such asdimethylformamide or N-methylpyrrolidone; an ether such astetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperatureis generally between 50° C. and 150° C.; utilizing as catalysts organicderivatives of palladium including palladium acetate,tetrakis(triphenylphosphine)palladium(0) or Pd₂ (dibenzylideneacetone)₃, generally in the presence of a base such as an alkalinehydroxide or carbonate acetate ion or an amine.

According to still another method of preparation of compound of formula(I), a compound of formula (II) is caused to react in the presence of acatalyst as described above, with a hexaalkylstannane [(alkyl orcycloalkyl)₃ Sn]₂ so as to form a compound of formula (V): ##STR7##

which in a second step is caused to react with a compound of formula(IV) in the presence of a coupling catalyst.

The first step of the process is generally conducted in an organicsolvent, for example an hydrocarbon such as toluene or xylene; an amidesuch as dimethylformamide or N-methylpyrrolidone; an ether such astetrahydrofuran, dimethoxyethane or 2-methoxyethylether; at atemperature generally between 50° C. and 150° C.; utilizing as catalystsorganic derivatives of palladium including palladium acetate,tetrakis(triphenylphosphine)palladium(0) or Pd₂ (dibenzylideneacetone)₃.

The second step of this second process is generally conducted in anorganic solvent, for example an hydrocarbon such as toluene or xylene;an amide such as dimethylformamide or N-methylpyrrolidone; an ether suchas tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; thetemperature is generally between 50° C. and 150° C.; as catalysts,organic derivatives of palladium such as Pd (P-phenyl 3)₄, Pd₂(dibenzylidene acetone)₃, Pd (O--CO--CH₃)₂ may be cited.

According to still another method of preparation of compound of formula(I), a compound of formula (II) is caused to react with a compound offormula (VII) ##STR8##

preferably in the presence of a coupling catalyst as described above,and referably in a solvent as described above, and preferably at atemperature from 50° C. to 150° C.

According to another method of preparation of a compound of formula (I),a compound of formula (VM): ##STR9##

is reacted in a step to form a pyrrole, imidazole, triazole, or pyrazoleof formula (I). Such reactions are known and can be found in Katritzky,Rees, and Scriven, Comprehensive Heterocyclic Chemistry II, volumes2,3,4 1996, Pergamon Press, London.

The invention is illustrated by the following examples, which are notconsidered as limiting the invention but are given to better enable useof it.

EXAMPLE 1

Preparation of1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-Cyano-4-trifluoromethylthio-5-aminopyrazole

A mixture of 6 g of5-amino-3-cyano-1-(2,6-dichloro-4-bromophenyl)-4-trifluoromethylthiopyrazole(prepared according to procedures reported in U.S. Pat. No. 5,232,940),4-trifluoromethylphenylboronic acid (5.3 g), K₂ CO₃ (5.8 g),tris-(dibenzylidene acetone) dipalladium (0.6 g) and diglyme was heatedat 130° C. for 25 hours. After cooling to 20° C., the mixture was pouredinto water and extracted with diethyl ether. The ether solutions werecombined, dried, filtered and the filtrate concentrated and purified bychromatography. The desired product as a solid (3.9 g, mp 181-184° C.)was obtained.

EXAMPLE 2

Preparation of1-[2,6-dichloro4-(4-trifluoromethylphenyl)phenyl]-3-cyano-4-trifluoromethylsulfonyl-5-aminopyrazole

A solution of1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole(0.5 g), m-chloroperbenzoic acid (2.2 g) and 1,2-dichloro-ethane washeated at reflux for 40 hours. After cooling to 20° C., the mixture wasdissolved in diethyl ether and washed with sat. aqueous NaHCO₃ solutiontwice, then saturated aqueous NaHSO₃ solution twice, dried, filtered,and the filtrate concentrated and purified by chromatography. Thedesired product as a solid (0.13 g, mp 197-202° C.) was obtained.

EXAMPLE 3

Preparation of1-[2,6-dichloro-4-(tributyltin)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole.

A mixture of1-(2,6-dichloro-4-bromophenyl)-3-cyano-4-trifluoromethylthio-5-aminopyrazole(5 g), bis-(tributyltin) (6.7 g), tetrakis(tri-phenylphosphine)palladium(0) (1.3 g) and 1-methyl-2-pyrrolidinone was heated to reflux for 75minutes, cooled to 20° C., poured to water and extracted with methylt-butyl ether. After concentrattion to dryness, methylene chloride wasadded and stirred with saturated aqueous KF solution for 16 hours. Morewater was added and extracted with methylene chloride. The methylenechloride solutions were combined, dried, filtered and the filtrateconcentrated and purified via chromatography. The desired product as asolid (1.9 g, mp 116-117° C.) was obtained.

EXAMPLE 4

Preparation of1-[2,6-dichloro4-(2,3,5,6-tetrafluoropyrid-4-yl)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole.

A mixture of1-[2,6-dichloro-4-(tributyltin)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole(0.5 g), 4-bromo-2,3,5,6-tetrafluoropyridine (0.1 mL),tetrakis(tri-phenylphosphine) palladium (0) (0.1 g) and THF was refluxedfor 26 hours. After cooling to 20° C., methylene chloride was added andstirred with saturated aqueous KF solution for 16 hours. The mixture wasfiltered with diethyl ether and dried, filtered again and the filtrateconcentrated and purified via chromatography. The desired product as asolid (87 mg, mp 100-104° C.) was obtained.

EXAMPLE 5

Preparation of1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-5-aminopyrazole.

A mixture of 1-(2,6-dichloro-4-bromophenyl)-3-cyano-5-aminopyrazole (45g, prepared according to procedures reported in U.S. Pat. No.5,232,940), 4-trifluoromethylphenylboronic acid (45 g), 2 M of Na₂ CO₃(75 mL), tris-(dibenzylideneacetone) dipalladium (6.4 g), toluene andethanol was heated at 130° C. for 25 hours. After cooling to 20° C., themixture was poured into water and extracted with diethyl ether. Theether solutions were combined, dried, filtered and the filtrateconcentrated and purified via chromatography. The desired product as asolid (30.6 g, mp 195-199° C.) was obtained.

EXAMPLE 6

Preparation of 1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-4-bromo-5-aminopyrazole.

A mixture of1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-5-aminopyrazole(1 g), N-bromosuccinimide (0.5 g) and acetonitrile was stirred at 20° C.for 90 minutes, then concentrated and the residue was mixed with diethylether, washed with saturated aqueous NaHCO₃ solution, dried, filteredand the filtrate concentrated and purified via chromatography. Thedesired product as a solid (1.04 g, mp 178-180° C.) was obtained.

EXAMPLE 7

Preparation of4-dichlorofluoromethylsulfenyl-1-[2-fluoro-4-(4-trifluoromethylphenyl)phenyl]imidazole.

Step A

A solution of 4-bromo-2-fluoroaniline (3.8 g) in 20 ml of triethylorthoformate was stirred at room temperature. After stirring for 1 h,tetrahydrofuran (40 ml), aminoacetonitrile hydrochloride (2.8 g), anddiisopropylamine (5.3 ml) were added and stirring continued for anadditional hour. After 1 h, the mixture was poured into 150 ml of icewater and extracted with 150 ml of dichloromethane. The organic solutionwas washed twice with water and dried over magnesium sulfate.Evaporation of solvents afforded a light purple solid (3.1 g), which waswashed with hexane and filtered.

The solid was dissolved in 40 ml of dichloromethane at reflux, cooled toroom temperature, and treated with tetramethylguanidine (1.6 ml), addeddropwise over twenty minutes. After stirring at room temperatureovernight, the mixture was cooled in an ice/salt bath anddichlorofluoromethylsulfenyl chloride (1.5 ml) was added. After 1 h, themixture was diluted with 100 ml of methylene chloride and washed withsaturated sodium bicarbonate solution, then with water, then dried overmagnesium sulfate. After filtration and evaporation, chromatography onsilica gel afforded5-amino-4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole(1.285 g).

Step B

1 g of5-amino-4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazolewas dissolved in 15 ml of tetrahydrofuran, cooled to 0° C., and treatedwith t-butylnitrite. After 1 h, the mixture is evaporated. Silca gelchromatography afforded4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole(0.555 g).

Step C

50 mg of4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole and37 mg of trifluoromethylphenylboronic acid in 3 ml of toluene weretreated with 0.13 ml of 2M aqueous potassium carbonate and a catalyticamount (about 5 mg) of palladium tetrakis(triphenylphoshine). Themixture was heated at 90° C. for 12 h, then cooled to room temperatureand evaporated. Silica gel chromatography afforded4-dichlorofluoromethylsulfenyl-1-[2-fluoro-4-(4-trifluoromethylphenyl)phenyl]imidazole(27.3 mg, mass spec mn/e 438).

In a manner similar to that employed in examples 1 to 7, the followingcompounds in Tables 1-4 were also prepared. The last column of the tableindicates the physical characteristic of the compound obtained from themass spectrum analysis. It is the m/e value from the mass spectrum ofthe molecular ion. The number of the compound is for identificationonly.

N/A=Not Applicable

AroCH is [4--OH 3-methoxy phenyl]--CH, so that AroCH═N-- is the group[4--OH 3-methoxy

                                      TABLE 1                                     __________________________________________________________________________     ##STR10##                                                                    CMP. NO                                                                            R12                                                                              R13                                                                              R15                                                                              R16                                                                              R22 R23 R24  R25                                                                              R26                                                                              R3  R4     R5     m/e                     __________________________________________________________________________     1   Cl H  H  Cl (CH═CH)2                                                                          H    H  H  CN  SCF3   NH2    478                      2   Cl H  H  Cl H   H   H    H  H  CN  SCF3   NH2    428                      3   Cl H  H  Cl Me  H   H    H  H  CN  SCF3   NH2    442                      4   Cl H  H  Cl H   NH2 H    H  H  CN  SCF3   NH2    443                      5   Cl H  H  Cl H   NO2 H    H  H  CN  SCF3   NH2    473                      6   Cl H  H  Cl H   NHAc                                                                              H    H  H  CN  SCF3   NH2    485                      7   Cl H  H  Cl H   CHO H    H  H  CN  SCF3   NH2    456                      8   Cl H  H  Cl H   H   OMe  H  H  CN  SCF3   NH2    458                      9   Cl H  H  Cl H   H   SMe  H  H  CN  SCF3   NH2    474                      10  Cl H  H  Cl H   H   F    H  H  CN  SCF3   NH2    446                      11  Cl H  H  Cl H   F   H    H  H  CN  SCF3   NH2    446                      12  Cl H  H  Cl H   Cl  F    H  H  CN  SCF3   NH2    480                      13  Cl H  H  Cl H   H   Cl   H  H  CN  SCF3   NH2    462                      14  Cl H  H  Cl H   H   Br   H  H  CN  SCF3   NH2    506                      15  Cl H  H  Cl H   Cl  H    Cl H  CN  SCF3   NH2    496                      16  Cl H  H  Cl H   H   CF3  H  H  CN  SCF3   NH2    496                      17  Cl H  H  Cl H   CF3 H    CF3                                                                              H  CN  SCF3   NH2    564                      18  Cl H  H  Cl (CH═CH)2                                                                          H    H  H  CN  SMe    NH2    424                      19  Cl H  H  Cl H   H   H    H  H  CN  SMe    NH2    374                      20  Cl H  H  Cl Me  H   H    H  H  CN  SMe    NH2    388                      21  Cl H  H  Cl H   NH2 H    H  H  CN  SMe    NH2    389                      22  Cl H  H  Cl H   NO2 H    H  H  CN  SMe    NH2    419                      23  Cl H  H  Cl H   NHAc                                                                              H    H  H  CN  SMe    NH2    431                      24  Cl H  H  Cl H   H   CHO  H  H  CN  SMe    NH2    402                      25  Cl H  H  Cl H   H   OMe  H  H  CN  SMe    NH2    404                      26  Cl H  H  Cl H   F   H    H  H  CN  SMe    NH2    392                      27  Cl H  H  Cl H   Cl  F    H  H  CN  SMe    NH2    426                      28  Cl H  H  Cl Cl  H   Cl   H  H  CN  SMe    NH2    442                      29  Cl H  H  Cl H   H   CF3  H  H  CN  SMe    NH2    442                      30  Cl H  H  Cl H   CF3 H    CF3                                                                              H  CN  SMe    NH2    510                      31  Cl H  H  Cl H   Br  H    H  H  CN  SMe    NH2    452                      32  Cl H  H  Cl Me  H   H    H  H  CN  SCF3   Van-CH═N--                                                                       576                      33  Cl H  H  Cl H   NO2 H    H  H  CN  SCF3   Van-CH═N--                                                                       607                      34  Cl H  H  Cl H   NHAc                                                                              H    H  H  CN  SCF3   Van-CH═N--                                                                       619                      35  Cl H  H  Cl H   H   CHO  H  H  CN  SCF3   Van-CH═N--                                                                       590                      36  Cl H  H  Cl H   H   OMe  H  H  CN  SCF3   Van-CH═N--                                                                       592                      37  Cl H  H  Cl H   Cl  F    H  H  CN  SCF3   Van-CH═N--                                                                       614                      38  Cl H  H  Cl Cl  H   Cl   H  H  CN  SCF3   Van-CH═N--                                                                       630                      39  Cl H  H  Cl H   H   CF3  H  H  CN  SCF3   Van-CH═N--                                                                       630                      40  Cl H  H  Cl H   H   CF3  H  H  CN  S(O)2CCl2F                                                                           NH2    560                      41  Cl H  H  Cl H   H   CF3  H  H  CN  S(O)2CCl2F                                                                           NH2    544                      42  Cl H  H  Cl H   H   CF3  H  H  CN  SCCl2F NH2    528                      43  Cl H  H  Cl H   H   CF3  H  H  CN  SOCF3  NH2    512                      44  Cl H  H  Cl H   H   CF3  H  H  CN  S(O)2CF3                                                                             NH2    528                      45  Cl H  H  Cl H   H   CF3  H  H  PhC(O)                                                                            SCF3   NH2    575                      46  Cl H  H  Cl (CH═CH)2                                                                          H    H  H  CN  SCF3   H      463                      47  Cl H  H  Cl H   (CH═CH)2                                                                           H  H  CN  SCF3   H      463                      48  Cl H  H  Cl H   H   H    H  H  CN  SCF3   H      413                      49  Cl H  H  Cl H   NO2 H    H  H  CN  SCF3   H      458                      50  Cl H  H  Cl H   H   OMe  H  H  CN  SCF3   H      443                      51  Cl H  H  Cl H   H   SMe  H  H  CN  SCF3   H      459                      52  Cl H  H  Cl H   H   F    H  H  CN  SCF3   H      431                      53  Cl H  H  Cl H   F   H    H  H  CN  SCF3   H      431                      54  Cl H  H  Cl H   Cl  F    H  H  CN  SCF3   H      465                      55  Cl H  H  Cl H   H   Cl   H  H  CN  SCF3   H      447                      56  Cl H  H  Cl H   H   Br   H  H  CN  SCF3   H      491                      57  Cl H  H  Cl H   Cl  H    Cl H  CN  SCF3   H      481                      58  Cl H  H  Cl Cl  H   Cl   H  H  CN  SCF3   H      481                      59  Cl H  H  Cl H   H   CF3  H  H  CN  SCF3   H      481                      60  Cl H  H  Cl H   CF3 H    H  H  CN  SCF3   H      481                      61  Cl H  H  Cl H   CF3 H    CF3                                                                              H  CN  SCF3   H      549                      62  Cl H  H  Cl H   Cl  H    H  H  CN  SCF3   H      447                      63  Cl H  H  Cl H   Br  H    H  H  CN  SCF3   H      491                      64  Cl H  H  Cl H   H   CF3  H  H  PhC(O)                                                                            S(O)2CCl2F                                                                           NH2    639                      65  Cl H  H  Cl H   H   Br   H  H  CN  SCCl2F NH2    538                      66  Cl H  H  Cl Cl  H   CF3  H  Cl CN  SCF3   NH2    564                      67  Cl H  H  Cl H   H   OCF3 H  H  CN  SCF3   NH2    512                      68  Cl H  H  Cl H   H   CF3  H  H  PhC(O)                                                                            S(O)2CClF2                                                                           NH2    623                      69  Cl H  H  Cl H   H   CF3  H  H  CN  H      NH2    396                      70  Cl H  H  Cl H   H   CF3  H  H  CN  Br     NH2    474                      71  Cl H  H  Cl H   H   CF3  H  H  CN  SEt    NH2    456                      72  Cl H  H  Cl H   H   CF3  H  H  CN  SMe    NH2    442                      73  Cl H  H  Cl H   H   CF3  H  H  CN  SCN    NH2    453                      74  Cl H  H  Cl H   H   CF3  H  H  CN  Cl     NH2    430                      75  Cl H  H  Cl H   H   CF3  H  H  CN  SOMe   NH2    458                      76  Cl H  H  Cl H   H   CF3  H  H  CN  S(O)E( NH2    472                      77  Cl H  H  Cl H   H   Br   H  H  CN  S(O)2CCl2F                                                                           NH2    570                      78  Cl H  H  Cl H   H   CF3  H  H  CN  S(O)2CH3                                                                             NH2    474                      79  Cl H  H  Cl H   H   CF3  H  H  CN  S(O)2Et                                                                              NH2    488                      80  Cl H  H  Cl H   H   CF3  H  H  CONH2                                                                             C(OH)(CF3)2                                                                          NH2    580                      81  Cl H  H  Cl H   H   CF3  H  H  CN  C(OH)(CF3)2                                                                          NH2    562                      82  Cl H  H  Cl H   H   CF3  H  H  CN  H      NHAC   438                      83  Cl H  H  Cl H   H   CF3  H  H  Ac  SMe    NH2    459                      84  Cl H  H  Cl H   H   CF3  H  H  CN  CF(CF3)2                                                                             NH2    564                      85  Cl H  H  Cl H   H   CF3  H  H  CN  SCCl2F H      513                      86  Cl H  H  Cl H   H   CF3  H  H  CN  S(O)2CCl2F                                                                           H      545                      87  Cl H  H  Cl H   Cl  Cl   H  H  CN  H      NH2    396                      88  Cl H  H  Cl H   H   OCF3 H  H  CN  H      NH2    412                      89  Cl H  H  Cl F   H   H    H  H  CN  H      NH2    346                      90  Cl H  H  Cl H   H   CO2Me                                                                              H  H  CN  H      NH2    386                      91  Cl H  H  Cl H   Cl  Cl   H  H  CN  SCF3   NH2    496                      92  Cl H  H  Cl F   H   H    H  H  CN  SCF3   NH2    446                      93  Cl H  H  Cl H   H   CO2Me                                                                              H  H  CN  SCF3   NH2    486                      94  Cl H  H  Cl H   H   CF3  H  H  CN  SCCl2F Br     591                      95  Cl H  H  Cl H   H   CF3  H  H  Ac  S(O)2CH3                                                                             NH2    491                      96  Cl H  H  Cl Cl  H   H    H  Cl CN  SCF3   NH2    496                      97  Cl H  H  Cl Cl  H   Cl   H  H  CN  SCF3   NH2    496                      98  Cl H  H  Cl Cl  H   CF3  H  Cl CN  SCF3   NH2    564                      99  Cl H  H  Cl CF3 H   H    H  H  CN  SCF3   NH2    496                     100  Cl H  H  Cl NO2 H   CF3  H  H  CN  SCF3   NH2    541                     101  Cl H  H  Cl Me  H   F    H  H  CN  SCF3   NH2    460                     102  Cl H  H  Cl H   F   H    F  H  CN  SCF3   NH2    464                     103  Cl H  H  Cl F   H   H    H  F  CN  SCF3   NH2    464                     104  Cl H  H  Cl H   OCF3                                                                              H    H  H  CN  SCF3   NH2    512                     105  Cl H  H  Cl H   F   H    Cl H  CN  SCF3   NH2    480                     106  Cl H  H  Cl H   CN  H    H  H  CN  SCF3   NH2    453                     107  Cl H  H  Cl H   OMe H    H  H  CN  SCF3   NH2    458                     108  Cl H  H  Cl H   H   CH2CN                                                                              H  H  CN  SCF3   NH2    467                     109  Cl H  H  Cl H   H   Me   H  H  CN  SCF3   NH2    506                     110  Cl H  H  Cl H   H   SO2NH2                                                                             H  H  CN  SCF3   NH2    507                     111  Cl H  H  Cl H   H   NMe2 H  H  CN  SCF3   NH2    471                     112  Cl H  H  Cl OCH2O   H    H  H  CN  SCF3   NH2    472                     113  Cl H  H  Cl H   H   CN   H  H  CN  SCF3   NH2    453                     114  Cl H  H  Cl H   H   CN   H  H  CN  SCF3   NH2    453                     115  Cl H  H  Cl F   H   F    H  H  CN  SCF3   NH2    464                     116  Cl H  H  Cl H   H   CONH2                                                                              H  H  CN  SCF3   NH2    471                     117  Cl H  H  Cl H   Cl  CN   H  H  CN  SCF3   NH2    487                     118  Cl H  H  Cl H   CF3 H    H  H  CN  SCF3   NH2    496                     119  Cl H  H  Cl F   F   F    F  F  CN  SCF3   NH2    518                     120  Cl H  H  Cl H   H   OPh  H  H  CN  SCF3   NH2    520                     121  Cl H  H  Cl Cl  H   CF3  H  H  CN  SCF3   NH2    530                     122  Cl H  H  Cl H   OCF2O    H  H  CN  SCF3   NH2    508                     123  Cl H  H  Cl H   F   NH2  H  H  CN  SCF3   NH2    461                     124  Cl H  H  Cl H   CF3 NO2  H  H  CN  SCF3   NH2    541                     125  Cl H  H  Cl OH  H   H    H  H  CN  SCF3   NH2    444                     126  Cl H  H  Cl H   H   NH2  H  H  CN  SCF3   NH2    443                     127  Cl H  H  Cl H   H   OH   H  H  CN  SCF3   NH2    444                     128  Cl H  H  Cl H   CF3 H    NH2                                                                              NH2                                                                              CN  SCF3   NH2    526                     129  Cl H  H  Cl H   F   Me   H  H  CN  SCF3   NH2    460                     130  Cl H  H  Cl CN  F   H    H  H  CN  SCF3   NH2    471                     131  Cl H  H  Cl H   Me  F    H  H  CN  SCF3   NH2    460                     132  Cl H  H  Cl Me  H   H    F  H  CN  SCF3   NH2    460                     133  Cl H  H  Cl Ph  H   H    H  H  CN  SCF3   NH2    504                     134  Cl H  H  Cl OH  OMe H    CHO                                                                              H  CN  SCF3   NH2    502                     135  Cl H  H  Cl H   Cl  Cl   H  H  CN  S(O)2CH3                                                                             NH2    474                     136  Cl H  H  Cl Cl  H   H    H  Cl CN  S(O)2CH3                                                                             NH2    474                     137  Cl H  H  Cl Cl  H   Cl   H  H  CN  S(O)2CH3                                                                             NH2    474                     138  Cl H  H  Cl Cl  H   CF3  H  Cl CN  S(O)2CH3                                                                             NH2    542                     139  Cl H  H  Cl H   H   OCF3 H  H  CN  S(O)2CH3                                                                             NH2    490                     140  Cl H  H  Cl CF3 H   H    H  H  CN  S(O)2CH3                                                                             NH2    474                     141  Cl H  H  Cl NO2 H   CF3  H  H  CN  S(O)2CH3                                                                             NH2    519                     142  Cl H  H  Cl Me  H   F    H  H  CN  S(O)2CH3                                                                             NH2    438                     143  Cl H  H  Cl H   F   H    F  H  CN  S(O)2CH3                                                                             NH2    442                     144  Cl H  H  Cl F   H   H    H  F  CN  S(O)2CH3                                                                             NH2    442                     145  Cl H  H  Cl F   H   H    H  H  CN  S(O)2CH3                                                                             NH2    424                     146  Cl H  H  Cl H   H   CF3  H  H  CN  C═NOH                                                                            NH2    439                     147  Cl H  H  Cl H   H   CF3  H  H  CN  NO2    NHAc   483                     148  Cl H  H  Cl H   H   CF3  H  H  CN  NO2    NH2    441                     149  Cl H  H  Cl F   H   F    H  H  CN  S(O)2CH3                                                                             NH2    442                     150  Cl H  H  Cl H   OCF3                                                                              H    H  H  CN  S(O)2CH3                                                                             NH2    490                     151  Cl H  H  Cl H   F   H    Cl H  CN  S(O)2CH3                                                                             NH2    458                     152  Cl H  H  Cl H   H   CONH2                                                                              H  H  CN  S(O)2CH3                                                                             NH2    449                     153  Cl H  H  Cl H   CN  H    H  H  CN  S(O)2CH3                                                                             NH2    431                     154  Cl H  H  Cl H   H   SMe  H  H  CN  S(O)2CH3                                                                             NH2    452                     155  Cl H  H  Cl H   OMe H    H  H  CN  S(O)2CH3                                                                             NH2    436                     156  Cl H  H  Cl H   H   CH2CN                                                                              H  H  CN  S(O)2CH3                                                                             NH2    445                     157  Cl H  H  Cl H   H   Ms   H  H  CN  S(O)2CH3                                                                             NH2    484                     158  Cl H  H  Cl H   H   SO2NH2                                                                             H  H  CN  S(O)2CH3                                                                             NH2    485                     159  Cl H  H  Cl H   H   NMe2 H  H  CN  S(O)2CH3                                                                             NH2    449                     160  Cl H  H  Cl OCH2O   H    H  H  CN  S(O)2CH3                                                                             NH2    450                     161  Cl H  H  Cl H   Cl  CN   H  H  CN  S(O)2CH3                                                                             NH2    465                     162  Cl H  H  Cl H   H   CN   H  H  CN  S(O)2CH3                                                                             NH2    431                     163  Cl H  H  Cl H   H   CO2Me                                                                              H  H  CN  S(O)2CH3                                                                             NH2    464                     164  Cl H  H  Cl H   CF3 H    H  H  CN  S(O)2CH3                                                                             NH2    474                     165  Cl H  H  Cl F   F   F    F  F  CN  S(O)2CH3                                                                             NH2    496                     166  Cl H  H  Cl H   H   OPh  H  H  CN  S(O)2CH3                                                                             NH2    498                     167  Cl H  H  Cl Cl  H   CF3  H  H  CN  S(O)2CH3                                                                             NH2    508                     168  Cl H  H  Cl Cl  H   5F5  H  Cl CN  S(O)2CH3                                                                             NH2    600                     169  Cl H  H  Cl Cl  H   OCF3 H  Cl CN  S(O)2CH3                                                                             NH2    558                     170  Cl H  H  Cl H   OCF2O    H  H  CN  S(O)2CH3                                                                             NH2    486                     171  Cl H  H  Cl H   CO2H                                                                              OH   H  H  CN  S(O)2CH3                                                                             NH2    466                     172  Cl H  H  Cl H   F   OH   H  H  CN  S(O)2CH3                                                                             NH2    440                     173  Cl H  H  Cl H   F   NH2  H  H  CN  S(O)2CH3                                                                             NH2    439                     174  Cl H  H  Cl H   CF3 NO2  H  H  CN  S(O)2CH3                                                                             NH2    519                     __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR11##                                                                    CMP. NO                                                                            R12                                                                              R13                                                                              R15                                                                              R16                                                                              R2 R22 R23 R24                                                                              R25                                                                              R26                                                                              R3    R4  R5 m/e                         __________________________________________________________________________    175  Cl H  H  Cl H  (CH═CH)2                                                                          H  H  H  SCFCl2                                                                              CN  Cl 528                         176  Cl H  H  Cl Cl H   (CH═CH)2                                                                         H  H  CN    SCFCl2                                                                            H  528                         177  Cl H  H  Cl Cl H   H   H  H  H  CN    SCFCl2                                                                            H  478                         178  Cl H  H  Cl H  H   H   Me H  H  SCFCl2                                                                              CN  Cl 492                         179  Cl H  H  Cl H  Me  H   H  H  H  SCFCl2                                                                              CN  Cl 492                         180  Cl H  H  Cl Cl H   NH2 H  H  H  CN    SCFCl2                                                                            H  493                         181  Cl H  H  Cl H  H   NO2 H  H  H  SCFCl2                                                                              CN  Cl 523                         182  Cl H  H  Cl Cl H   NHAc                                                                              H  H  H  CN    SCFCl2                                                                            H  535                         183  Cl H  H  Cl H  CHO H   H  H  H  SCFCl2                                                                              CN  Cl 506                         184  Cl H  H  Cl H  H   CHO H  H  H  SCFCl2                                                                              CN  Cl 506                         185  Cl H  H  Cl Cl H   H   CHO                                                                              H  H  CN    SCFCl2                                                                            H  506                         186  Cl H  H  Cl H  OMe H   H  H  H  SCFCl2                                                                              CN  Cl 508                         187  Cl H  H  Cl H  H   OMe H  H  H  SCFCl2                                                                              CN  Cl 508                         188  Cl H  H  Cl Cl H   H   OMe                                                                              H  H  CN    SCFCl2                                                                            H  508                         189  Cl H  H  Cl Cl H   H   SMe                                                                              H  H  CN    SCFCl2                                                                            H  524                         190  Cl H  H  Cl H  H   H   F  H  H  SCFCl2                                                                              CN  Cl 496                         191  Cl H  H  Cl Cl H   F   H  H  H  CN    SCFCl2                                                                            H  496                         192  Cl H  H  Cl Cl H   Cl  F  H  H  CN    SCFCl2                                                                            H  530                         193  Cl H  H  Cl H  H   H   Cl H  H  SCFCl2                                                                              CN  Cl 512                         194  Cl H  H  Cl H  H   H   Br H  H  SCFCl2                                                                              CN  Cl 556                         195  Cl H  H  Cl Cl H   Cl  H  Cl H  CN    SCFCl2                                                                            H  546                         196  Cl H  H  Cl H  Cl  H   Cl H  H  SCFCl2                                                                              CN  Cl 546                         197  Cl H  H  Cl Cl H   H   CF3                                                                              H  H  CN    SCFCl2                                                                            H  546                         198  Cl H  H  Cl Cl H   CF3 H  H  H  CN    SCFCl2                                                                            H  546                         199  Cl H  H  Cl H  H   CF3 H  CF3                                                                              H  SCFCl2                                                                              CN  Cl 614                         200  Cl H  H  Cl Cl H   Cl  H  H  H  CN    SCFCl2                                                                            H  512                         201  Cl H  H  Cl Cl H   Br  H  H  H  CN    SCFCl2                                                                            H  556                         202  Cl H  H  Cl H  H   H   CF3                                                                              H  H  S(O)CFCl2                                                                           CN  Cl 562                         203  Cl H  H  Cl H  H   H   CF3                                                                              H  H  S(O)2CFCl2                                                                          CN  Cl 578                         204  H  H  H  H  H  H   H   CF3                                                                              H  H  CHO   H   H  315                         205  H  H  H  Me H  H   H   CF3                                                                              H  H  CHO   H   H  329                         206  Me H  H  Me H  H   H   CF3                                                                              H  H  CHO   H   H  343                         207  Cl H  H  H  H  H   H   CF3                                                                              H  H  CHO   H   H  349                         208  H  Cl H  H  H  H   H   CF3                                                                              H  H  CHO   H   H  349                         209  Cl H  H  Me H  H   H   CF3                                                                              H  H  CHO   H   H  363                         210  Cl H  H  Cl H  H   H   CF3                                                                              H  H  CHO   H   H  383                         211  F  H  H  H  H  H   H   CF3                                                                              H  H  CHO   H   H  333                         212  F  H  H  F  H  H   H   CF3                                                                              H  H  CHO   H   H  351                         213  H  H  H  CF3                                                                              H  H   H   CF3                                                                              H  H  CHO   H   H  383                         214  H  H  CF3                                                                              H  H  H   H   CF3                                                                              H  H  CHO   H   H  383                         215  F  F  F  F  H  H   H   CF3                                                                              H  H  CHO   H   H  387                         216  Me H  H  NO2                                                                              H  H   H   CF3                                                                              H  H  CHO   H   H  374                         217  H  H  (CH═CH)2                                                                        H  H   H   CF3                                                                              H  H  CHO   H   H  365                         __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________     ##STR12##                                                                    CMP. NO                                                                            R12                                                                              R13                                                                              R15                                                                              R16                                                                              R22                                                                              R23 R24                                                                              R25                                                                              R26                                                                              R3    R5 m/3                                 __________________________________________________________________________    218  Cl H  H  Cl H  H   CF3                                                                              H  H  t-Bu  NH2                                                                              428                                 219  Cl H  H  Cl H  H   CF3                                                                              H  H  t-Bu  H  413                                 220  Cl H  H  Cl H  H   CF3                                                                              H  H  t-Bu  Br 491                                 221  Cl H  H  Cl H  H   CF3                                                                              H  H  CF3   NH2                                                                              440                                 222  Cl H  H  Cl H  NO2 H  H  H  CF3   NH2                                                                              417                                 223  Cl H  H  Cl H  F   H  H  H  CF3   NH2                                                                              390                                 224  Cl H  H  Cl H  H   CF3                                                                              H  H  CF3   Br 503                                 225  Cl H  H  Cl H  H   CF3                                                                              H  H  CF3   H  425                                 226  Cl H  H  Cl H  (CH═CH)2                                                                         H  H  CF3   NH2                                                                              422                                 227  Cl H  H  Cl (CH═CH)2                                                                         H  H  H  CF3   NH2                                                                              422                                 228  Cl H  H  Cl Me H   H  H  H  CF3   NH2                                                                              386                                 229  Cl H  H  Cl H  OMe H  H  H  CF3   NH2                                                                              402                                 230  Cl H  H  Cl H  H   OMe                                                                              H  H  CF3   NH2                                                                              402                                 231  Cl H  H  Cl H  H   SMe                                                                              H  H  CF3   NH2                                                                              418                                 232  Cl H  H  Cl H  H   F  H  H  CF3   NH2                                                                              390                                 233  Cl H  H  Cl H  H   Cl H  H  CF3   NH2                                                                              406                                 234  Cl H  H  Cl H  H   Br H  H  CF3   NH2                                                                              450                                 235  Cl H  H  Cl H  Cl  H  Cl H  CF3   NH2                                                                              440                                 236  Cl H  H  Cl Cl H   Cl H  H  CF3   NH2                                                                              440                                 237  Cl H  H  Cl H  CF3 H  H  H  CF3   NH2                                                                              440                                 238  Cl H  H  Cl H  Cl  H  H  H  CF3   NH2                                                                              406                                 239  Cl H  H  Cl H  Br  H  H  H  CF3   NH2                                                                              450                                 240  Cl H  H  Cl (CH═CH)2                                                                         H  H  H  CF3   H  407                                 241  Cl H  H  Cl H  H   H  H  H  CF3   H  357                                 242  Cl H  H  Cl H  H   Me H  H  CF3   H  371                                 243  Cl H  H  Cl H  NO2 H  H  H  CF3   H  402                                 244  Cl H  H  Cl H  CHO H  H  H  CF3   H  385                                 245  Cl H  H  Cl H  OMe H  H  H  CF3   H  387                                 246  Cl H  H  Cl H  H   F  H  H  CF3   H  375                                 247  Cl H  H  Cl H  H   F  H  H  CF3   H  375                                 248  Cl H  H  Cl H  F   H  H  H  CF3   H  375                                 249  Cl H  H  Cl H  Cl  F  H  H  CF3   H  409                                 250  Cl H  H  Cl H  (CH═CH)2                                                                         H  H  CF3   H  407                                 251  Cl H  H  Cl H  NHAc                                                                              H  H  H  CF3   H  414                                 252  Cl H  H  Cl CHO                                                                              H   H  H  H  CF3   H  385                                 253  Cl H  H  Cl H  H   CHO                                                                              H  H  CF3   H  385                                 254  Cl H  H  Cl OMe                                                                              H   H  H  H  CF3   H  387                                 255  Cl H  H  Cl H  H   CF3                                                                              H  H  SMe   H  403                                 256  Cl H  H  Cl H  H   CF3                                                                              H  H  SMe   NH2                                                                              418                                 257  Cl H  H  Cl H  H   CF3                                                                              H  H  SOMe  NH2                                                                              434                                 258  Cl H  H  Cl H  H   CF3                                                                              H  H  SOMe  H  419                                 259  Cl H  H  Cl H  H   CF3                                                                              H  H  SOMe  Br 497                                 260  Cl H  H  Cl H  H   CF3                                                                              H  H  SCCl2F                                                                              H  489                                 261  Cl H  H  Cl H  H   CF3                                                                              H  H  S(O)CCl2F                                                                           H  505                                 263  Cl H  H  Cl H  H   CF3                                                                              H  H  S(O)2CCl2F                                                                          H  521                                 __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________     ##STR13##                                                                    CMP. NO                                                                            R12                                                                              R13                                                                              R15                                                                              R16                                                                              R21   R23  R24 R25                                                                              R26                                                                              R4    R5 m/3                            __________________________________________________________________________    264  Cl H  H  Cl H     H    CF3 H  H  SCCl.sub.2 F                                                                        H  488                            265  Cl H  H  Cl H     H    CF3 H  H  SCCl.sub.2 F                                                                        Br 566                            266  Cl H  H  Cl H     H    CF3 H  H  SCCl.sub.2 F                                                                        NH2                                                                              503                            267  Cl H  H  Cl H     H    CF3 H  H  SO.sub.2 CCl2F                                                                      Br 537                            268  Cl H  H  Cl H     H    CF3 H  H  SOCCl.sub.2 F                                                                       H  504                            269  Cl H  H  Cl H     H    CF3 H  H  SO2CCl2F                                                                            H  520                            270  H  H  H  F  H     H    CF3 H  H  SOCCl2F                                                                             H  454                            271  Cl H  H  Cl Cl    H    CF3 H  Cl SOCCl2F                                                                             H  572                            272  Cl H  H  Cl H     H    OCF3                                                                              H  H  SOCCl2F                                                                             H  520                            273  Cl H  H  Cl H     OCF2O    H  H  SOCCl2F                                                                             H  516                            274  Cl H  H  Cl H     H    H   H  H  SOCCl2F                                                                             H  436                            275  Cl H  H  Cl Me    H    Me  Me H  SOCCl2F                                                                             H  478                            276  Cl H  H  Cl Me    H    H   H  Me SOCCl2F                                                                             H  464                            277  Cl H  H  Cl H     H    t-Bu                                                                              H  H  SOCCl2F                                                                             H  492                            278  Cl H  H  Cl H     CF3  H   CF3                                                                              H  SOCCl2F                                                                             H  572                            279  Cl H  H  Cl H     CH2CN                                                                              H   H  H  SOCCl2F                                                                             H  475                            280  Cl H  H  Cl H     OCH2O    H  H  SOCCl2F                                                                             H  480                            281  Cl H  H  Cl H     F    H   F  H  SOCCl2F                                                                             H  472                            282  Cl H  H  Cl F     F    NH2 F  F  SOCCl2F                                                                             H  523                            283  Cl H  H  Cl NO2   H    CF3 H  H  SOCCl2F                                                                             H  549                            284  Cl H  H  Cl H     H    CH2CN                                                                             H  H  SOCCl2F                                                                             H  475                            285  Cl H  H  Cl H     H    n-Bu                                                                              H  H  SOCCl2F                                                                             H  492                            286  Cl H  H  Cl Cl    H    Cl  H  H  SOCCl2F                                                                             H  504                            287  Cl H  H  Cl H     NO2  NH2 Me Me SOCCl2F                                                                             H  524                            288  Cl H  H  Cl Cl    H    CF3 H  H  SOCCl2F                                                                             H  538                            289  Cl H  H  Cl Cl    H    Cl  H  Cl SOCCl2F                                                                             H  538                            290  Cl H  H  Cl F     F    CF3 F  F  SOCCl2F                                                                             H  576                            291  Cl H  H  Cl F     F    CN  F  F  SOCCl2F                                                                             H  533                            292  Cl H  H  Cl 5-tetrazolyl                                                                        H    H   H  H  SOCCl2F                                                                             H  504                            293  Cl H  H  Cl H     H    CN  H  H  SOCCl2F                                                                             H  461                            294  Cl H  H  Cl Cl    H    SF5 H  Cl SOCCl2F                                                                             H  630                            295  H  H  H  F  H     H    CF3 H  H  SCCl2F                                                                              H  438                            296  Cl H  H  Cl H     H    CF3 H  H  SCF3  H  456                            297  Cl H  H  Cl H     H    CF3 H  H  SOCF3 H  472                            298  Cl H  H  Cl H     H    CF3 H  H  SO.sub.2 CF3                                                                        H  488                            __________________________________________________________________________

The present invention provides also a method for controlling pests at alocus comprising applying to said locus a pesticidally effective amountof a compound of formula (I), or a pesticidal composition comprising apesticidally effective amount of a compound of formula (I) and apesticidally acceptable carrier therefor. In a preferred embodiment, theinvention provides a method for controlling insects at a locuscomprising applying to said locus an insecticidally effective amount ofa compound of formula (I), or an insecticidally effective amount of aninsecticidal composition comprising an insecticidally effective amountof a compound of formula (I) and an agriculturally acceptable inertcarrier therefor. Preferably, the locus to which the pesticidally(especially insecticidally) effective amount is applied is acrop-growing area, that is, an area in which a crop is growing or inwhich a crop has been planted, or an area in which a crop will beplanted/grown.

The compositions which can be used in the invention for thepesticidal/insecticidal treatment of the invention can comprise fromabout 0.001 to 95% of the compound of formula (I).

The diluted liquid formulations, as applied to the locus to be treatedor crop, generally comprise from about 0.001 to about 3% of activeingredient of formula (I), preferably from about 0.1 to about 0.5%.

The solid formulations as applied to the locus or crop generallycomprise from about 0.1 to about 8% of active ingredient of formula (I),preferably from about 0.5 to about 1.5%.

The concentrated compositions are the compositions which arecommercialized or transported or stored. For application to plants, theyare normally diluted in water and applied in such diluted form. Thediluted forms are part of the invention as well as the concentratedforms.

The concentrated formulations generally comprise from about 5 to about95% of active ingredient of formula (I), preferably from about 10 toabout 50%.

The insecticidal compositions of the invention can be applied once, ormore than once, throughout the whole insect season. Insecticidalcompositions according to the invention are usually applied to the locusto be treated or crop area at a rate of from about 0.01 to about 2 kg/haof active ingredient, preferably from about 0.1 to about 1 kg/ha.

The concentrated insecticidal compositions according to the inventioncan be in the form of a solid, e.g., dusts or granules or wettablepowders, or, preferably, in the form of a liquid, such as anemulsifiable concentrate or a true solution.

The compositions according to the instant invention generally comprisefrom about 0.5 to about 95% of active ingredient of formula (I). Theremainder of the composition up to 100% comprises a carrier as well asvarious additives such as those hereafter indicated.

By "carrier", there is meant herein an organic or inorganic material,which can be natural or synthetic, and which is associated with theactive ingredient and which facilitates its application to the locus tobe treated or crop. This carrier is thus generally inert and should beagriculturally acceptable, especially on the contemplated or treatedlocus or crop. The carrier can be solid (clay, silicates, silica,resins, wax, fertilizers, etc.) or liquid (water, alcohols, ketones, oilsolvents, saturated or unsaturated hydrocarbons, chlorinatedhydrocarbons, liquified petroleum gas, etc.).

Among the many additives, the compositions of the invention can comprisesurfactants as well as other ingredients such as dispersants, stickers,antifoam agents, antifreezing agents, dyestuffs, thickeners, adhesives,protective colloids, penetrating agents, stabilizing agents,sequestering agents, antiflocculating agents, corrosion inhibitors,pigments and polymers.

More generally, the compositions of the invention can comprise all kindsof solid or liquid additives which are known in the art of insecticidesand insecticidal treatments.

The surfactants can be of the emulsifying or wetting type, ionic ornon-ionic. Possible surfactants are salts of polyacrylic orlignosulfonic acids; salts of phenolsulfonic or naphthalenesulfonicacids; polycondensates of ethylene oxide with fatty alcohols or fattyacids or fatty amines or substituted phenols (particularly alkylphenolsor arylphenols); ester-salts of sulfosuccinic acids; taurinederivatives, such as alkyl taurates; phosphoric esters; or esters ofalcohols or polyoxyethylated phenols. When the spraying vehicle iswater, the use of at least one surfactant is generally required becausethe active ingredients are not water-soluble.

The method of application of the compositions of the invention isgenerally the spraying of a mixture which has been previously made, bydilution of more concentrated formulations according to the invention.

Solid compositions can be powders for dusting or for dispersion (whereinthe content of active ingredient can be up to 100%) and granules,especially extruded or compacted granules, or granules which have beenmade by impregnation of a powder (the content of active ingredient insuch powders being between about 1 and about 80%).

Liquid compositions or compositions which have to be liquid when appliedinclude solutions, water-soluble concentrates, emulsifiableconcentrates, emulsions, wettable powders or pastes or water-dispersiblegranules.

Emulsifiable concentrates generally comprise from about 10 to about 80%of active ingredient; the emulsions when applied generally comprise fromabout 0.01 to about 20% of active ingredient.

For example, the emulsifiable concentrates can comprise the solvent and,to the extent needed, from about 2 to about 20% of suitable additivessuch as stabilizers, surfactants, penetrating agents, corrosioninhibitors or other additives already recited.

These concentrates are usually diluted in tank water so as to obtain thedilution appropriate for spraying.

The concentrated suspensions can also be applied by spraying and have tobe fluid without allowing any solid to separate and fall to the bottom.Generally they comprise from about 1 to about 75% of active ingredient(preferably from about 2 to about 50%), from about 0.5 to about 15% ofsurfactant, from about 0.1 to about 10% of thickener, from 0 to about10% of other suitable additives as already indicated, the remainderbeing water or an organic liquid wherein the active ingredient isinsoluble or has a low solubility.

The wettable powders generally comprise the active ingredient (fromabout 1 to about 95%, preferably from about 2 to about 80%), the solidcarrier, a wetting agent (from 0 to about 5%), a dispersing agent (fromabout 3 to about 10%) and, to the extent needed, from 0 to about 10% ofother additives such as stabilizers and others as already listed.

In order to obtain these wettable powders or dusting powders, it isappropriate to intimately mix the active ingredients and the additives,as by grinding in a mill or similar device.

Dispersible granules are generally made by agglomeration of a powder,followed by an appropriate granulation process.

The emulsions herein described can be of the oil-in-water orwater-in-oil types. Fluidity of the emulsions can range from lowviscosities up to high viscosities approaching those of gels.

Among these many compositions or formulations, one skilled in the artcan choose the one most appropriate, according to the specificconditions of the treatment problem.

The compounds and compositions of the invention can also be used inadmixtures with another pesticide, e.g., an insecticide, acaricide orherbicide.

The compounds of the invention may also be used in controlling pestsfound in non-agricultural domains.

In the field of veterinary medicine or livestock husbandry or in themaintenance of public health against arthropods, helminths or protozoawhich are parasitic internally or externally upon vertebrates,particularly warm-blooded vertebrates, for example man or domesticanimals, e.g. cattle, sheep, goats, equines, swine, poultry, dogs orcats, for example Acarina, including ticks (e.g. Ixodes spp., Boophilusspp. e.g. Boophilus microplus, Amblyomma spp., Hyalomma spp.,Rhipicephalus spp. e.g. Rhipicephalus appendiculatus, Haemaphysalisspp., Dermacentor spp., Ornithodorus spp. (e.g. Ornithodorus moubata)and mites (e.g. Damalinia spp., Dermahyssus gallinae, Sarcoptes spp.e.g. Sarcoptes scabiei, Psoroptes spp., Chorioptes spp;, Demodex spp.,Eutrombicula spp.,); Diptera (e.g. Aedes spp., Anopheles spp.,Dermatobia spp., Haematobia spp., Musca spp., Hippoboscidae spp.,Hypoderma spp., Gasterophilus spp., Simulium spp); Stomoxys spp.,Hemiptera (e.g. Triatoma spp); Phthirapter (e.g. Damalinia spp.,Linognathus spp.); Siphonaptera (e.g. Ctenocephalides spp.); Dictyoptera(e.g. Periplaneta spp., Blatella spp.); Hymenoptera (e.g. Monomoriumpharaonis); for example against infections of the gastro-intestinaltract caused by parasitic nematode worms, for example members of thefamily Trichostrongylidae, Nippostrongylus brasiliensis, Trichinellaspiralis, Haemonchus contortus, Trichostrongylus colubriformis,Nematodirus batus, Ostertagis circumcincta, Trichostrongylus axei,Cooperia spp. and Hymenolepis nana; in the control and treatment ofprotozoal diseases caused by, for example, Eimeria spp. e.g. Eimeriatenella, Eimeria acervulina, Eimeria brunetti, Eimeria maxima andEimeria necatrix, Trypanosoms cruzi, Leishaminia spp., Plasmodium spp.,Babesis spp., Trichomonadidae spp., Histomanas spp., Giardia spp.,Toxoplasma spp., Entamoeba histolytica and Theileria spp.

Furthermore the compounds of the invention may be useful forcoccidiosis, a disease caused by infections from protozoan parasites ofthe genus Eimeria.

Compositions

Solid or liquid compositions for application topically to animals,timber, stored products or household goods usually contain from about0.00005% to about 90%, more particularly from about 0.001% to about 10%,by weight of one or more compounds of general formula (I). Foradministration to animals orally or parenterally, includingpercutaneously solid or liquid compositions, these normally contain fromabout 0.1% to about 90% by weight of one or more compounds of generalformula (I). Medicated feedstuffs normally contain from about 0.001% toabout 3% by weight of one or more compounds of general formula (I).Concentrates or supplements for mixing with feedstuffs normally containfrom about 5% to about 90%, preferably from about 5% to about 50%, byweight of one or more compounds of general formula(I). Mineral saltlicks normally contain from about 0.1% to about 10% by weight of one ormore compounds of general formula (I).

Dusts or liquid compositions for application to livestock, persons,goods, premises or outdoor areas may contain from about 0.0001% to about15%, more especially from about 0.005% to about 2.0%, by weight, of oneor more compounds of general formula (I). Suitable concentrations intreated waters are between about 0.0001 ppm and about 20 ppm, moreparticularly about 0.001 ppm to about 5.0 ppm of one or more compoundsof general formula (I) and may be used therapeutically in fish fanningwith appropriate exposure times. Edible baits may contain from about0.01% to about 5%, preferably from about 0.01% to about 1.0%, by weight,of one or more compounds of general formula (I).

When administered to vertebrates parenterally, orally or by percutaneousor other means, the dosage of compounds of general formula (I) willdepend upon the species, age, or health of the vertebrate and upon thenature and degree of its actual or potential infestation by arthropod,helminth or protozoan pests. A single dose of about 0.1 to about 100 mg,preferably about 2.0 to about 20.0 mg, per kg body weight of the animalor doses of about 0.01 to about 20.0 mg, preferably about 0.1 to about5.0 mg, per kg body weight of the animal per day, for sustainedmedication, are generally suitable by oral or parenteral administration.By use of sustained release formulations or devices, the daily dosesrequired over a period of months may be combined and administered toanimals on a single occasion.

The following methods were used to apply the compounds of the inventionand to observe the results obtained therewith: a foliar/contact spray onsucking (aphids) or chewing (Lepidoptera) insects.

The species tested were as follows:

    ______________________________________                                        GENUS, SPECIES     COMMON NAME                                                ______________________________________                                        Aphis gossypii     cotton leaf aphid                                          Musca domestica    housefly                                                   Diabrotica virgifera                                                                             Western cornrootworm                                       Periplaneta americana                                                                            American Cockroaches                                       Spodoptera eridania                                                                              Southern armyworm                                          ______________________________________                                    

The Housefly Bait/Contact Test

About 25 four to six-day-old adult houseflies were anesthetized andplaced in a cage with a sugar water bait solution containing thecompound. The concentration of the selected compound of formula (I) inthe bait solution was 50 ppm. After 24 hours, flies which showed nomovement on stimulation were considered dead.

Foliar application (Contact Test) with Aphids

Aphid-infested cotton plants were placed on a revolving turntable, andsprayed to runoff with a 100 ppm formulation of the selected compound offormula (I). The treated, A. gossypii-infested plants were held forthree days after treatment, after which the dead aphids were counted.

Application on Western cornrootworm

Jars are filled with 60 g dry soil homogeneously mixed with 5 ml aqueoussolution containing the compound to be tested. After drying, fourgerminated corn seedlings are placed in the bottom of each jar and thesoil is wetted. Then ten newly born larvae are placed in each jar. Thejars are stored for six days at 27° C. under 70% of relative humidity.The number of surviving larvae are then counted.

Application by contact to Cockroaches

The inner wall of a 100 ml jar is covered by shaking 2 ml of pesticidalformulation. Furthermore, a pellet of dog chow is placed into a jar andthe pesticidal formulation is absorbed on the pellet, using excessliquid. The jar is then left open up to evaporation of liquid. Cockroachnymphs are placed in the jar and mortality is assessed after five days.

Application to Southern armyworm

Leaves of soybeans were sprayed to run-off with a spray of variousconcentrations. Then the leaves were allowed to dry, excised, and placedinto a container with five larvae. The containers are stored for fivedays at 25° C. under 50% relative humidity. Mortality ratings are thencounted.

Application to Caenorhabditis elegans (nematode worm)

This test is significative for animal health applications of activeingredient. Test formulation are prepared by mixing 2 microliters ofdimethylsulfoxide with 100 microliters of a solution of Escherichia Coli(which is food for C.elegans). 98 microliters of this mixture are thenmixed with an inoculum solution which consists of mixed life stages ofC.Elegans (about 50 worms). This new mixture is stored 7 days at 20° C.Mortality is then visually assessed as well as the behavior of the worm.For the mortality, the rating is either 1 (large increase in number ofthe population, similar to the control which is trebbling in 7 days) or3 (slight increase of the population, but significantly less increasethan the control) or 5 (little to no increase in the population). Forthe behavior effect, the rating is either 1 (normal motion) or 3 (motionis slower than the control) or 5 (little to no movement).

All the hereinabove prepared compounds show a positive activity in oneor more of these tests (rather good activity on C. elegans).

While the invention has been described in terms of various preferredembodiments, the person skilled in the art will appreciate that variousmodifications, substitutions, omissions and changes can be made withoutdeparting from the spirit thereof. Accordingly, it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims, including equivalents thereof.

What is claimed is:
 1. A compound having the formula: ##STR14## wherein:R₂ is H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy,haloalkoxy, CN, NO₂, --S(O)_(n) R₈, alkylcarbonyl, alkoxycarbonyl,aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,hydroxycarbonyl, aminosulfonyl, alkylaminosulfonyl, ordialkylaminosulfonyl;R₃ is CN; R₄ is --S(O)_(n) R₈ ; R₅ is hydrogen,halogen, --NR₉ R₁₀, --N═CR₁₁ R₁₉, --S(O)_(n) R₈, formyl, alkylcarbonyl,haloalkylcarbonyl, cyano, alkyl, haloalkyl, hydrazino, alkoxycarbonyl,alkylthiocarbonyl, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl; R₈ is alkyl,haloalkyl, alkenyl, or alkynyl, or R₈ is a cycloalkyl ring having 3 to 5carbon atoms; R₁₁ is H or alkyl; R₁₉ is hydrogen, alkyl, haloalkyl,alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, or dialkylamino;or R₁₉ is phenyl, thienyl, pyridyl or furyl, each of which isunsubstituted or substituted with one or more substituents selected fromthe group consisting of alkyl, haloalkyl, halogen, NO₂, CN, alkoxy,haloalkoxy, OII, alkylcarbonyl and alkylcarbonyloxy; R₉ and R₁₀,independently of each other, are H, alkyl, haloalkyl, alkylcarbonyl,haloalkylcarbonyl, R₈ S(O)_(n), formyl, alkenyl, alkynyl,alkoxycarbonyl, alkylthiocarbonyl, or aroyl; or R₉ and R₁₀ are joined soas to together form a divalent radical having 4 to 6 atoms in the chain,said divalent radical being alkylene, alkyleneoxyalkylene oralkyleneaminoalkylene, the alkyl portions of R₉ and R₁₀ being optionallysubstituted by R₇ ; R₇ is cyano, nitro, alkoxy, haloalkoxy, R₈ S(O)_(n),--C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl, --CO₂ H, halogen, hydroxy, aminosulfonyl,alkylaminosulfonyl or dialkylaminosulfonyl; Z is N or C--R₁₆ ; n iszero, one or two; R₁₂, R₁₃, R₁₅ and R₁₆ independently of one another,are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro,amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl,alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl,formyl, alkylcarbonyl or alkoxycarbonyl; and R₂₂, R₂₃, R₂₄, R₂₅, andR₂₆, independently of one another, are hydrogen, halogen, allyl,haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy,haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide,alkoxycarbonyl, SF₅, or R₈ S(O)_(n) ; or R₂₂ and R₂₃ or R₂₃ and R₂₄ orR₂₅ and R₂₆ together form divinylidene (CH═CH CH═CH--), methylenedioxy(--O--CH₂ --O--) or difluoromethylenedioxy (--O--CF₂ --O--) so as toform a cyclic ring vicinal to the phenyl ring; or a pesticidallyacceptable salt thereof.
 2. A compound according to claim 1, havingformula (Ia).
 3. A compound according to claim 1, wherein R₉ and R₁₀ arejoined together to form with the adjacent nitrogen atom a morpholine,pyrrolidine, piperidine or piperazine ring, optionally substituted byR₇.
 4. A compound according to claim 1, wherein R₂₄ is halogen,haloalkyl or haloalkoxy.
 5. A compound according to claim 1, wherein R₅is --NR₉ R₁₀.
 6. A compound according to claim 5, wherein R₅ is --NH₂.7. A compound according to claim 1, wherein R₈ is lower alkyl orhaloalkyl.
 8. A compound according to claim 1, having at least onefeature selected from the group consisting of:R₅ is hydrogen, halogen,C₁ -C₃ alkyl, C₁ -C₋₋ haloalkyl, or --NR₉ R₁₀ ; R₈ is methyl, ethyl,--CF₃, --CFCl₂, or --CF₂ Cl; R₁₂ and R₁₆, independently of each other,are F, Cl, Br or H; R₁₃ and R₁₅ are H; R₂₄ is --CF₃, OCF₃, --CHF₂,--S(O)_(n) CF₃, --CFCl₂, --CF₂ Cl, --OCF₂ Cl, -OCFCl₂, Cl, Br or F; andZ is CCl, CF, CBr or N.
 9. A compound according to claim 1, wherein theS(O)_(n) R₈ substituent of formula (Ia) or (Ib) is: methylthio,methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl,ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio,cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl,isopropylthio, trifluoromethylthio, trifluoromethylsulfinyl,trifluoromethylsulfonyl, dichlorofluoromethylthio,dichlorofluoromethylsulfinyl, dichlorofluoromethylsulfonyl,chlorodifluoromethylthio, chlorodifluoromethylsulfonyl orchlorodifluoromethylsulfinyl.
 10. A compound according to claim 8,wherein the S(O)_(n) R₈ substituent of formula (Ia) or (Ib) is:trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl,dichlorofluoromethylthio, dichlorofluoromethylsulfinyl,dichlorofluoromethylsulfonyl, chlorodifluoromethylthio,chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
 11. Thecompound of formula (Ia) according to claim 2, which is4-dichlorofluoromethylsulfenyl1-[2-fluoro-4-(4-trifluoromethylphenyl)phenyl]imidazole.
 12. Apesticidal composition comprising:(a) a pesticidally effective amount ofa compound having the formula: ##STR15## wherein: R₂ is H, halogen,hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN, NO₂,--S(O)_(n) R₈, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl,aminosulfonyl, alkylaminosulfonyl, or dialkylaminosulfonyl; R₃ is CN; R₄is S(O)_(n) R₈ ; R₅ is hydrogen, halogen, --NR₉ R₁₀, --N═CR₁₁ R₁₉,--S(O)_(n) R₈, formyl, alkylcarbonyl, haloalkylcarbonyl, cyano, alkyl,haloalkyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-ylor 1H-pyrazol-1-yl: R₈ is alkyl, haloalkyl, alkenyl, or alkynyl, or R₈is a cycloalkyl ring having 3 to 5 carbon atoms; R₁₁ is H or alkyl; R₁₉is hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino,monoalkylamino, or dialkylamino; or R₁₉ is phenyl, thienyl, pyridyl orfuryl, each of which is unsubstituted or substituted with one or moresubstituents selected from the group consisting of alkyl, haloalkyl,halogen, NO₂, CN, alkoxy, haloalkoxy, OH, alkylcarbonyl andalkylcarbonyloxy; R₉ and R₁₀, independently of each other, are H, alkyl,haloalkyl, alkylcarbonyl, haloalkylcarbonyl R₈ S(O)_(n), formyl,alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, or aroyl; or R₉ andR₁₀ are joined so as to together form a divalent radical baying 4 to 6atoms in the chain, said divalent radical being alkylene,alkyleneoxyalkylene or alkyleneaminoalkylene the alkyl portions of R₉and R₁₀ being optionally substituted by R₇ ; R₇ is cyano, nitro, alkoxy,haloalkoxy, R₈ S(O)_(n), --C(O)alkyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, --CO₂ H, halogen, hydroxy,aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; Z is N orC--R₁₆,; n is zero, one or two; R₁₂, R₁₃, R₁₅ and R₁₆, independently ofone another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano,nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl,alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl,haloalkylsulfonyl, formyl, alkylcarbonyl or alkoxycarbonyl; and R₂₂,R₂₃, R₂₄, R₂₅, and R₂₆, independently of one another, are hydrogen,halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino,alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide,amide, alkoxycarbonyl, SF₅, or R₈ S(O)_(n) ; or R₂₂ and R₂₃ or R₂₃ andR₂₄ or R₂₅ and R₂₆ together form divinylidene (CH═CH--CH═CH--),methylenedioxy (--O--CH₂ --O--) or difluoromethylenedioxy (--O--CF₂--O--) so as to form a cyclic ring vicinal to the phenyl ring; or apesticidally acceptable salt thereof; and (b) a pesticidally acceptablecarrier thereof.
 13. A composition according to claim 12, wherein thecompound has formula (Ia).
 14. A composition according to claim 12,comprising from 0.001 to 95% of compound of formula (Ia) or (Ib).
 15. Acomposition according to claim 13, comprising from 0.001 to 95% ofcompound of formula (Ia).
 16. A method for controlling pests at a locuscomprising applying to said locus a pesticidally effective amount of acompound having the formula: ##STR16## wherein: R₂ is H, halogen,hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN, NO₂,--S(O)_(n) R₈, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl,aminosulfonyl, alkylaminosulfonyl, or dialkylaminosulfonyl;R₃ is CN; R₄is --S(O)_(n) R₈ ; R₅ is hydrogen, halogen, --NR₉ R₁₀, --N═CR₁₁ R₁₉,--S(O)_(n) R₈, formyl, alkylcarbonyl, haloalkylcarbonyl, cyano, alkyl,haloalkyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-ylor 1H-pyrazol-1-yl; R₈ is alkyl, haloalkyl, alkenyl, or alkynyl, or R₈is a cycloalkyl ring having 3 to 5 carbon atoms; R ₁₁ is H or alkyl; R₁₉is hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino,monoalkylamino, or dialkylamino; or R₁₉ is phenyl, thienyl, pyridyl orfuryl, each of which is unsubstituted or substituted with one or moresubstituents selected from the group consisting of alkyl, haloalkyl,halogen, NO₂, CN, alkoxy, haloalkoxy, OH, alkylcarbonyl andalkylcarbonyloxy; R₉ and R₁₀, independently of each other are H, alkyl,haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R₈ S(O)_(n), formyl,alkenyl, alkynyl, alkoxycarbonyl alkylthiocarbonyl, or aroyl; or R₉ andR₁₀ are joined so as to together form a divalent radical having 4 to 6atoms in the chain, said divalent radical being alkylene,alkyleneoxyalkylene or alkyleneaminoalkylene, the alkyl portions of R₉and R₁₀ being optionally substituted by R₇ ; R₇ is cyano, nitro, alkoxy,haloalkoxy, R₈ S(O)_(n), --C(O)alkyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, --CO₂ H, halogen, hydroxy,aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; Z is N orC--R₁₆ ; n is zero, one or two; R₁₂, R₁₃, R₁₅ and R₁₆, independently ofone another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano,nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl,alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl,haloalkylsulfonyl, formyl, alkylcarbonyl or alkoxycarbonyl; andR₂₂, R₂₃,R₂₄, R₂₅, and R₂₆, independently of one another, are hydrogen, halogen,alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy,haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide,alkoxycarbonyl, SF₅, or R₈ S(O)_(n) ; or R₂₂ and R₂₃ or R₂₃ and R₂₄ orR₂₅ and R₂₆ together form divinylidene (CH═CH--CH═CH--), methylenedioxy(--O--CH₂ --O--) or difluoromethylenedioxy (--O--CF₂ --O--) so as toform a cyclic ring vicinal to the phenyl ring; or a pesticidallyacceptable salt thereof.
 17. A method according to claim 16, wherein thecompound has formula (Ia).
 18. A method according to claim 16, whereinsaid pests are insects and wherein said pesticidally effective amount isan insecticidally effective amount.
 19. A method according to claim 17,wherein said pests are insects and wherein said pesticidally effectiveamount as an insecticidally effective amount.
 20. A method according toclaim 16, comprising applying to said locus from about 0.01 to about 2kg/ha of compound of formula (Ia) or (Ib).
 21. A method according toclaim 17, comprising applying to said locus from about 0.01 to about 2kg/ha of compound of formula (Ia).
 22. A method according to claim 20,comprising applying to said locus from about 0.1 to about 1 kg/ha ofcompound of formula (Ia) or (Ib).
 23. A method according to claim 21,comprising applying to said locus from about 0.1 to about 1 kg/ha ofcompound of formula (Ia).
 24. A method for controlling pests at a locuscomprising applying to said locus a pesticidally effective amount of acomposition as claimed in claim
 12. 25. A method for controlling pestsat a locus comprising applying to said locus a pesticidally effectiveamount of a composition as claimed in claim
 13. 26. A method accordingto claim 24, wherein said pests are insects and wherein saidpesticidally effective amount is an insecticidally effective amount. 27.A method according to claim 25, wherein said pests arc insects andwherein said pesticidally effective amount is an insecticidallyeffective.
 28. A process for preparing a compound of formula (Ia) or(Ib) according to claim 1, which comprises:(a) reacting a compound ofthe formula; ##STR17## wherein R₂, R₃, R₄, R₅, R₁₂, R₁₃, R₁₅ and Z areas defined in claim 1, with a boric acid or ester in the presence of acoupling catalyst to form a compound of the formula: ##STR18## whereinR₂, R₃, R₄, R₅, R₁₂, R₁₃, R₁₅ and Z are as defined in claim 1 and R₃₀ ishydrogen, alkyl, or divalent lower alkylene such that B(OR₃₀)₂ forms acyclic borate ester; followed by reacting the resultant compound offormula (IIIa) or (IIIb) with a compound of the formula: ##STR19##wherein R₂₂, R₃, R₂₄, R₂₅ and R₂₆ are as defined in claim 1 and R₂₀ isbromine, iodine or O--SO₂ CF₃ ; (b) reacting a compound of formula (IIa)or (IIb) above with a compound of formula (IV): ##STR20## wherein R₂₂,R₂₃, R₂₄, R₂₅, and R₂₆ are as defined in claim 1 and R₃₀ is as definedabove; (c) reacting a compound of formula (IIa) or (IIb) above with ahexaalkylstannane to form a compound of the formula: ##STR21## whereinR₂, R₃, R₄, R₅, R₁₂, R₁₃, R₁₅ and Z art as defined in claim 1; followedby reacting the resultant compound of formula (Va) or (Vb) with acompound of formula (IV) above in the presence of a coupling catalyst;or (d) reacting a compound of formula (IIa) or (IIb) above with acompound of formula (VI) above in the presence of a coupling catalyst.